Simultaneous dyeing of wool and cotton fibrous material with condensation product of formaldehyde and mixture of sulfones and hydroxybenzenesulfonic acids

ABSTRACT

THIS INVENTION PROVIDES A PROCESS FOR THE SIMULTANEOUS DYEING OF WOOL AND CELLULOSIC FIBROUS MATERIAL WITH WOOLAND SUBSTANTIVE DYESTUFFS IN THE PRESENCE OF A FIBRE-AFFINIC WOOL RESISTING AGENT AND HEXAMETHYLENETETRAMINE. THE WOOL RESISTING AGENTS USED ARE CONDENSATION PRODUCTS OF FORMALDEHYDE WITH A MIXTURE OF (A) SULFONES CONTAINING TWO HYDROXYBENZENE RESIDUES LINKED TO THE -SO2-GROUP AND (B) MONOCYCLIC HYDROXYBENZENESULFONIC ACIDS. BY THE PRESENT PROCESS THE DEPOSITION OF COTTON DYESTUFF ON THE WOOL FIBRE IS PREVENTED.

United States Patent U.S. Cl. 8-23 Claims ABSTRACT OF THE DISCLOSURE This invention provides a process for the simultaneous dyeing of wool and cellulosic fibrous material with wooland substantive dyestuffs in the presence of a fibre-affinic wool resisting agent and hexamethylenetetramine. The wool resisting agents used are condensation products of formaldehyde with a mixture of (a) sulfones containing two hydroxybenzene residues linked to the fiSO group and (b) monocyclic hydroxybenzenesulfonic acids. By the present process the deposition of cotton dyestuif on the wool fibre is prevented.

It is known that wool can be advantageously dyed with wool dyes and cellulosic fibres with substantive cotton dyes in one and the same bath, when dyeing is performed in baths that contain in addition to the dyestuffs fibreafiinic wool resisting agents and hexamethylenetetramine and which are of acid reaction at least at the start of the dyeing operation.

It has now been found that particularly valuable results are obtained when the wool resisting agent in the bath is a condensation product of formaldehyde and a mixture of (a) a sulphone containing two monocyclic benzene residues bound to the SO groups and further substituted by hydroxyl groups and (b) a monocyclic hydroxybenzenesulphonic acid.

According to this invention wool is dyed simultaneously with cellulosic fibrous material. Suitable cellulosic fibrous materials are regenerated cellulose, such as rayon or spun rayon, as well as native cellulose such as linen or especially cotton. These fibrous materials may be in different stages of their processing, for example loose or mixed yarns or in form of fabrics. They may be present in intimate mixtures, for example in mixed weaves, or the individual types of fibre may form large fibre combinations; this is the case, for example, in fabrics in which warp and weft consist of different types of material, or in carpets in which the pile and the backing are made from different materials. So-called half-wool is specially preferred; it consists of wool and cotton, and this mixture may be intimate or brought about only during the doubling or weaving operation.

The wool share is dyed with wool dyes which may belong to a variety of types, especially to the group of acid azo dyes or of the acid anthraquinone dyestufis. Among the azo dyes the monoazo dyes are specially suitable. Advantageous results have been obtained with chromium or cobalt complexes of monoazo dyes that contain more than ice one molecule of dyestnff for every atom of metal bound in complex union, and in which at least one dyestuif molecule is free from sulphonic acid groups and from carboxyl groups not participating in the complex formation. The heavy metal atom may be bound with two different or two identical dyestuif molecules. The complexforming group of the dyestuffs may be, for example, an orthcrhydroxy-ortho'-aminoazo grouping, an ortho-hydroxy-ortho'-carboxyazo grouping or preferably an ortho, ortho-dihydroxyazo grouping. A large number of this type of dyestuffs is known.

The cellulose fibres are dyed with substantive cotton dyestuffs which advantageously have as such little affinity for the wool fibre. Otherwise, these dyestuffs may belong to a variety of types. Thus, for example, there may be used azo dyes, especially disazo and polyazo dyes, which may contain metal bound in complex union, preferably copper, or azoxy dyestuffs or sulphonated copper phthalocyanines.

The condensation products to be used in the present process are prepared from mixtures of sulphones and sulphonic acids of the kind referred to above. Advantageously, mixtures are used in which the molecular ratio of (a) sulphone to (b) sulphonic acid is from 40:60 to :15. Both the sulphones and sulphonic acids suitable as relevant starting materials are known. From among the sulphones the dihydroxydiphenylsulphones of the formula Ha l- 0.

are preferred, in which R and R independently of each other, represent hydrogen atoms or methyl or sulphonic acid groups. As examples the following may be mentioned:

4,4-dihydroxy-diphenylsulphone, 4,2'-dihydroxy diphenylsulphone, 4,4'-dihydroxy-3,3-dimethyl-diphenylsulphone, 4,4'-dihydroxy-diphenylsulphone-3-sulphonic acid and more especially 4,4'-dihydroxy-3-methyl-diphenylsulphone.

Suitable monocyclic hydroxybenzenesulphonic acids are, for example, phenolsulphonic acid such as 1-hydroxybenzene-4-sulphonic acid and cresolsulphonic acids sozn drox'ybenzene, such as phenol, p-cresol or a xylenol, with Manufacturing instruction concentrated sulphuric acid; then water is added and the alkaline reaction is adjusted by addition of the requisite A miXtl-lffi f 317 gof Y Y- ll p .quantity of alkali metal hydroxide, and without intery p and 150-5 E- y yy mediate separation the condensation with formaldehyde 5 slllphonic acid in 100 f Wat is endered alkaline i f d, with 463 g. of 30% aqueous sodium hydroxide solution.

The amount of the condensation product described Then 162 of 37% aqueous fofmaldehyik 801115011 are above to b dd d to h d b h can vary i hi rather added and the reaction mixture is stirred for 5 to 6 hours wide limits and may be, for example, from 0.075 to 2%, 9- The fesllltillg condPnsafion p f y referred to the weight of the fibrous material to be dyed. 10 be diluted with Water m any desll'ed Proportion Wlthollt The amount of hexamethylenetetramine should be adapted y Prficipitate forming to the amount of condensation product and of acid, but Similar condensatic'n Products are Obialned w n here too there are still rather wide limits within which not only the process can be carried out but even specially 4,4 y y-dlphcnylsulphone,

good results are obtained. As a general guide rule it may 4,zfdihydmxy-dipfleaylsulPmPe be said that for every part of condensation product at least 4a4fdlhydroxy'3z3 dlmethyl'dlpheilylSflPhQm A: part and at most 5 parts of hexamethylenetetramine y yph nylsulphone-3 -sulphomc ac d or a Should be used. mixture of these sulphones together with The dyebath must have an acid reaction at least at the 1'hydroxy'z'methylbenzene'ii'sul?hqmc and or start of the dyeing operation. The necessary acid reac- P 'f" 9 is reacted with form tion is advantageously adjusted by the addition of acetic aldehyde m the Indicated manner acid to the dyebath. Since hexamethylenetetramine con- Example tinuously gives off ammonia during dyeing, the pH value of the dyebath, and incidentally also of the wool, rises in course of time. However, with the quantities of acetic acid conventionally used in dyeing from acid baths it is quite possible to conduct the dyeing process so that even when dyeing takes a relatively long time the pH value never rises substantially above 7 so that it is possible to positively prevent any damage to the wool fibre caused by excess alkalinity.

In the present process the said condensation products prevent the substantive cotton dyestuffs from depositing on the wool. In most instances of dyeing half-wool it is endeavoured to achieve as even a tinctorial strength as possible for the two fibres; this is considerably facilitated in dyeing by the present process since the two fibres are (1) OH G A preparation is manufactured by mixing 1 part of the condensation product A with 2 parts of hexamethylenetetrarnine.

100 parts of half-wool (warp: viscose spun rayon; weft: pure wool boucle yarn) are immersed at 50 C. into a bath containing in 4000 parts of water parts of crystalline sodium sulphate, 2 parts of 40% acetic acid and 1 part of the preparation described above. The bath is kept for 15 minutes at C. and then a solution of the following two dyestufifs in a little water is added:

(a) 1:2-chromium complex of the dyestuif of the formula dyed at the same time. However, with all types of fibres t CN substantially only the dyestuff intended for the specific 01S I fibre deposits on it so that the wool dye is not fixed on 40 the cellulose fibre and the substantive cotton dyestutf is HiN Cl not fixed on the wool. CH:

The present process has the advantage that, even when relatively small quantities of a readily accessible agent (b) dyestufl of the formula H033 C Ha 1103s NH Ho OCH:

are used, the deposition of the cotton dyestuif on the Within 30 minutes the bath is heated to the boil and wool fibre is substantially prevented so that it is possible the half-Wool is dyed for 1 hour at the boil. An even red to obtain from a single bath very clear tone-in-tone or dyeing is obtained. Shading additions of one or the other two-tone eifects. of the above dyestuffs may be made at any time in the To improve its wet fastness the dyed material may, if manner usual in dyeing without the dyeing becoming desired, be after-treated in known manner with an agent uneven. Dyestuft (a) has been fixed almost exclusively on that improves wet fastness properties, for example a conthe wool and dyestuif (b) almost exclusively on the spun densation product of dicyandiamide with formaldehyde. rayon.

Instead of adding the condensation product and hexa- Instead of the above combination of dyestuffs (a) and methylenetetramine separately to the dyebath, the above- (b), the wool dyes shown in column I in combination with mentioned quantities of these substances may be admixed the appropriate substantive dyestuffs in column II of the to form stable preparations ready for use and suitable for following table may be used in the indicated manner for the performance of the present process. Such preparations dyeing half-wool, whereby either on both fibres the same are added in an amount from 0.1 to 10%, referred to the shades (Nos. 1 to 6) or very clean two-tone effects (Nos. 7 weight of the fibrous material to be dyed. to 10) are obtained.

Parts and percentages in the following Manufacturing If desired, the two constituents of the preparation may Instruction and in the example are by weight. be added at the same ratio singly to the dyebath.

TABLE-Continued Shade N o. (1) W001 dye 11. Chromium compound in which one molecule each of the dyestuffs Substantive dyestutl oi the composition shown above sub 10/11.... Wool: grey; cellulose:

12... Wool dye of the composition shown above sub 11/I-- .-.mu..." Dyestuff of Formula 15. W00]: grey; cellulose: red.

What is claimed is:

1. The process for the simultaneous dyeing of wool and cotton material, the wool being dyed with wool dyestuffs and the cellulosic fibrous material with substantive cotton dyestufi's, in dyebaths that are of acid reaction at least at the start of the dyeing operation and which contain a fiber-alfinic Wool resisting agent and hexamethylenetetramine, which process comprises adding as wool resisting agent to the dyebath a condensation product of (1) formaldehyde and (2) a mixture of (a) sulfones containing two monocyclic benzene residues which are bound with the -SO group and are further substituted by hydroxyl groups, and

(b) phenolsulfonic acids or cresolsulfonic acids.

2. The process according to claim 1, wherein the sulfones (a) are of the formula in which R; and R independently of each other, represent a member selected from the group consisting of hydrogen atoms, methyl and sulfonic acid groups.

3. The process according to claim 1, wherein the monocyclic hydroxybenzenesulfonic acids (b) are selected from the group consisting of phenolsulfonic acids and cresolsulfonic acids.

14. The process according to claim 1, wherein the condensation products of the indicated kind contain (a) 4,4- dihydroxy 3 methyl-diphenylsulfonic-(1,1) and (b) 1-hydroxy-2-methylbenzene-4-sulfonic acid.

5. The process according to claim 1, wherein the molecular ratio of (a) sulfone to (b) sulfonic acid in the condensation products of the indicated kind is 40:60 to References Cited UNITED STATES PATENTS 3,118,723 1/1964 Harding 8-14 3,290,111 12/1966 Hees et a1 8-165 3,298,774 1/ 1967 Soiron et a1. 8-43 X 3,075,822 1/1963 Abel 8-23 FOREIGN PATENTS 680,862 10/ 1952 Great Britain 8-14 GEORGE F. LESMES, Primary Examiner P. C. IVES, Assistant Examiner US. Cl. X-R- 

